Phosphonium phenoxide catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids

ABSTRACT

Certain tetrahydrocarbyl phosphonium phenoxide salts are described herein which are novel compounds and/or novel catalysts for promoting the reaction between vicinal epoxides and phenols and/or carboxylic acids or anhydrides. These catalysts are particularly useful in preparing high molecular weight epoxy resins by the advancement reaction of diglycidyl ether of bisphenol A with bisphenol A.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 148,875, filed May 12,1980, now U.S. Pat. No. 4,302,574, issued Nov. 24, 1981, which is acontinuation-in-part of application Ser. No. 041,567, filed May 23,1979, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel tetrahydrocarbyl phosphonium phenoxidesalts and the preparation of new epoxy-containing materials by a processemploying these and other salts as catalysts. In one preferredembodiment, this invention pertains to a process for making a linear,polymeric material having a molecular weight of at least about 100,000from the advancement reaction of an epoxy resin with a polyhydric phenol(specifically bisphenol A) in the presence of a tetrahydrocarbylphosphonium bisphenoxide salt.

This invention also relates to precatalyzed epoxy resins andprecatalyzed polyhydric phenolic compositions comprising, respectively,an epoxy resin having an average of more than one vicinal epoxide groupper molecule or a polyhydric phenol, each composition containing atetrahydrocarbyl phosphonium phenoxide salt catalyst for promoting thereaction between an epoxide and a phenolic hydroxyl group.

2. Prior Art

It is well-known in the art to produce hydroxyl-containing ethers byreacting a vicinal epoxide with a compound bearing phenolic hydroxyls inthe presence of such catalysts as tertiary amines, quaternary ammoniumhalides, phosphonium halides and the like. See, for example: U.S. Pat.Nos. 2,216,099; 2,633,458; 2,658,855; 3,377,406; 3,477,990; 3,547,881;3,547,885; 3,694,407; 3,738,862; 3,948,855; and 4,048,141. Canadian Pat.No. 893,191, German Pat. DT Nos. 2,206,218 and 2,335,199 and the text,Handbook of Epoxy Resins by H. Lee and K. Neville, McGraw-Hill (1967),Epoxy Resins-Chemistry and Technology, Edited by C. Maynard and Y.Tanaka, Marcel-Dekker, Inc. (1973) are also of interest. It is alsotaught in U.S. Pat. No. 4,048,141 that certain phosphonium catalystspromote the reaction between vicinal epoxides and phenols and/orcarboxylic acids or anhydrides.

The prior art catalysts for promoting reactions of epoxides with phenolshave generally been deficient in one or more aspects. In many instances,the catalysts react with the epoxy reactant and thus preclude themarketing of a blend comprising an epoxy resin and a catalyst, aso-called "precatalyzed epoxy resin". Blends comprising a polyhydricphenol and a catalyst (i.e., a precatalyzed polyhydric phenol) havelikewise been avoided due to possible adverse reactions of the twocomponents. Many prior art catalysts exhibit a lack of selectivity inthat they simultaneously promote the reaction of an epoxy resin withboth the phenolic hydroxyl group(s) on the reactant and the aliphatichydroxyl group(s) on the product, which produces branched orcross-linked polymers rather than the desired linear polymers. In stillother instances, the reaction rate is unsatisfactory and/or the productis highly colored or contaminated with corrosive anions (e.g.,chloride). Moreover, vinyl ester resins made from the catalyzed reactionproducts of epoxy resins and polyhydric phenols in the presence of mostprior art catalysts require undesirably long cure times because of thepresence of relatively high concentrations of phenolic hydroxyl groups.

The prior art catalysts, to a greater or lesser degree, produce at bestlinear or substantially linear polymers of relatively limited molecularweights. For example, the advancement reaction of4,4'-isopropylidenediphenol (i.e., bisphenol A) with a diglycidyl etherof bisphenol A in the presence of a triphenyl ethyl phosphonium acetatesalt-acetic acid complex even when followed by further reaction withtetrabromobisphenol A produces a linear polymer with a maximum weightaverage molecular weight of about 60,000 as determined by gel permeationchromatography. These deficiencies have now been remedied by the subjectinvention.

SUMMARY OF THE INVENTION

It has now been discovered that tetrahydrocarbyl phosphonium phenoxidesalts represented by the formula ##STR1## wherein R₁ -R₄ eachindependently is a hydrocarbyl or inertly-substituted hydrocarbyl, "X"is a phenoxide anion, and "m" is the valence of the anion "X", are novelcatalysts for promoting the reaction between vicinal epoxides andcarboxylic acids or anhydrides or aromatic compounds bearing nuclearhydroxyl groups.

The term phenoxide as used herein denotes a conjugate base of anaromatic carbocyclic compound bearing at least one nuclear hydroxylgroup. The tetrahydrocarbyl phosphonium phenoxide salts include thosesalts complexed with one or more moles of an aromatic carbocyclichydroxyl compound H_(m) X, wherein X and m are defined as above. Thesesalts also include salts complexed with one or more moles of atetrahydrocarbyl phosphonium hydroxide salt.

These novel catalysts are surprisingly effective in selectivelycatalyzing the desired reaction at a suitable reaction rate. Reactionproducts can be obtained in high conversion and are of excellent color.When the novel compound represented by Formula I, in which X is derivedfrom a polyhydric phenol is used as an advancement catalyst, linearreaction products can be prepared with weight average molecular weightssubstantially exceeding those effected by prior art methods.

Additionally, the novel catalysts are surprisingly unreactive with epoxyresins or polyhydric phenols at conventional storage temperatures. As aresult, a precatalyzed epoxy resin or polyhydric phenol can be prepared,respectively, by blending the subject catalyst with an epoxy resin orpolyhydric phenol. Such precatalyzed epoxy resins or polyhydric phenolsare, of course, novel compositions of matter.

DETAILED DESCRIPTION OF THE INVENTION Phosphonium Phenoxide Salts

Representative tetrahydrocarbyl phosphonium phenoxide salts arerepresented by formula II or IV. Phenol complexes of these salts arerepresented by formula III and V-VII. In formulae II-VII, R₁ -R₄ and Xare defined as in Formula I.

    R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕ X.sup.⊖II

    R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕ X.sup.⊖.HX III

    (R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕).sub.2 X.sup. IV

    (R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕).sub.2 X.sup. .H.sub.2 X V

    (R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕).sub.2 X.sup. .2H.sub.2 X VI

    (R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕).sub.2 X.sup. .3H.sub.2 X VII

Where the phenoxide anion is derived from a monohydric phenol, thetetrahydrocarbyl phosphonium phenoxide salt may take the formrepresented by formulae II or III. If X is derived from a dihydricphenol, the possible compounds are represented by formulae II-VII. Ofcourse, other salts and complexes are possible where the phenoxide anionis derived from a trihydric aromatic hydroxyl compound or a higherpolyhydric aromatic hydroxyl compound. We believe that formula IIrepresents the typical phosphonium phenoxide salts.

The tetrahydrocarbyl phosphonium phenoxide salts complexed withtetrahydrocarbyl phosphonium hydroxide salts have the following formula,wherein R₁ -R₄ and X are as previously defined,

    R.sub.1 R.sub.2 R.sub.3 R.sub.4 P.sup.⊕ X.sup.⊖.P.sup.⊕ R.sub.1 R.sub.2 R.sub.3 R.sub.4 OH.sup.⊖.

Generally, such complexes have been observed where X is a monoanionderived from a dihydric or polyhydric phenol.

The phenoxide anion, X, is a conjugate base of a phenol or otheraromatic carbocyclic hydroxyl compound, said phenol being an organiccompound having an aromatic mono- or polycyclic hydrocarbon nucleusbearing one or more hydroxyl groups. The phenoxide anion, phenoxidedianion and higher phenoxide anions are distinguished from thecorresponding phenol or other aromatic hydroxyl compounds in that one ormore of the phenolic or other aromatic hydroxyl groups are deprotonatedin the former. The phenoxide anion can be generally represented by theformula ##STR2## wherein each W independently is an oxide anion,hydrogen, carboxyl, halo, hydrocarbyl, nitro or hydroxyl moiety. Where Wis a hydrocarbon substituent it can bear or contain one or more benzenerings bearing phenolic hydroxyl, phenoxide anion, halo, nitro, hydrogenor carboxyl moieties.

Representative phenoxide anions include conjugate bases of phenol, α-and β-naphthol, o-, m-, or p-chlorophenol, 2-hydroxybiphenyl, alkylatedderivatives (e.g., o-methyl-, 3,5-dimethyl-, p-t-butyl- andp-nonylphenol), other monohydric phenols, or a halogenated or nitratedderivative thereof, as well as polyhydric phenols, such as resorcinol,hydroquinone, phenolphthalein, etc. In one embodiment, the phenoxideanion, X, can be the conjugate base of an epoxy resin bearing at leastone terminal phenolic hydroxyl group. Where the phosphonium phenoxidesalt is utilized as a catalyst for the advancement of a polyepoxide, theanion, X, is desirably a conjugate base of the phenol to be reacted withthe polyepoxide reactant.

Tetrahydrocarbyl phosphonium salts of polyhydric phenols are novelcompounds, which are preferred as catalysts. Preferred phenoxide anionsand phenoxide dianions are those which are conjugate bases anddiconjugate bases, respectively, of polyhydric phenols bearing from 2 to6 nuclear hydroxyl groups and having from about 12 to about 30 carbonatoms, because the novel phosphonium salts containing these anions areparticularly effective as catalysts in preparing ultra-high molecularweight epoxy resins. Representative examples of such preferred anionsinclude the phenoxides and bisphenoxides of phenolphthalein,2,4',4"-tri(hydroxyphenyl)methane (i.e., trisphenol) and the compoundcorresponding to the formula ##STR3##

Particularly preferred are the conjugate bases and diconjugate bases ofpolyhydric phenols corresponding to the formula ##STR4## wherein each Rindependently is a hydrogen, halogen, hydrocarbyl, inertly-substitutedhydrocarbyl or hydrocarbyloxy group, and Y is a single covalent bond,oxygen, sulfur, --CO--, --SO--, --SO₂ --, lower alkylene or alkylideneof from 1 to 6 carbon atoms, inclusive. In one embodiment, Y is ahydrocarbon radical consisting essentially ofoxyarylene-oxy(1,3-(2-hydroxy)alkylene units, so that the comound offormula VIII is an epoxy resin prepolymer terminated with two phenolichydroxyl groups, said prepolymer having a substantially linear backbone.More preferably, each R independently is hydrogen, chlorine or bromineand Y is a C₁ -C₄ alkylene or alkylidene; most preferably, Y ismethylene or isopropylidene. The most preferred phenoxide anions anddianions are those derived from bisphenol A(4,4'-isopropylidenediphenol), bisphenol F (4,4'-methylenediphenol),2,2',6,6'-tetrachlorobisphenol A, 2,2',6,6'-tetrabromobisphenol A,bisphenol S (4,4'-sulfonyldiphenol) and2,2',6,6'-tetrabromo-4,4'-sulfonyldiphenol.

In both the salts and the complexes, R₁ -R₄ independently are preferablyphenyl, benzyl, alkyl or inertly-substituted alkyl of from 1 to 12carbon atoms and more preferably are phenyl or a C₁ -C₄ alkyl.Illustrative examples of the instant class of novel compounds include:tetraphenyl-, triphenyl methyl-, triphenyl ethyl-, triphenyl n-butyl-,triphenyl benzyl-, tetra-n-butyl-, tri-n-butyl methyl-, tri-n-butylbenzyl, tri-(cyanoethyl)methyl-, tri-(hydroxymethyl)methyl-phosphoniumphenoxide salts, the analogous di(tetrahydrocarbylphosphonium)bisphenoxide salts or phenolic complexes of said salts andthe like. More preferably R₁ -R₄ are each independently phenyl orn-butyl groups. Most preferably these tetrahydrocarbyl groups aretriphenyl n-butyl or triphenyl ethyl groups.

Compounds of formula I are conveniently prepared by reacting, at atemperature of about 0° C. to 25° C., a tetrahydrocarbyl phosphoniumhalide dissolved in a lower alkanol, water or mixtures thereof with anion-exchange resin of the quaternary ammonium, hydroxide-type, tothereby produce a solution containing the corresponding tetrahydrocarbylphosphonium hydroxide salt. The reaction is most efficiently carried outby passing the phosphonium halide solution through a column packed withthe ion-exchange resin; however, a batchwise procedure can also be used.In an alternate procedure, the tetrahydrocarbyl phosphonium halide isreacted with an alkali metal hydroxide in a liquid medium to produce thetetrahydrocarbyl phosphonium hydroxide. A phenol is then added to thetetrahydrocarbyl phosphonium hydroxide solution, in generally astoichiometric ratio so as to produce a tetrahydrocarbyl phosphoniumphenoxide salt, or a phenol complex of said salt. Completion of thisreaction can be determined by monitoring the pH of the solution. Thephosphonium salt can be separated by filtration, if a precipitate, orthe solvent can be removed by distillation to recover the solid salt.

In still another process, the tetrahydrocarbyl phosphonium halide can bemixed with a phenol in a liquid medium followed by addition of an alkalimetal hydroxide to produce the tetrahydrocarbyl phosphonium phenoxidesalt or a phenol complex of said salt. This latter method is the methodof choice for preparing the preferred tetrahydrocarbyl phosphoniumcatalysts having phenoxide or bisphenoxide anions, such as those derivedfrom bisphenol A.

If 0.5 mole of a phenol is reacted with each mole of thetetrahydrocarbyl phosphonium hydroxide, a tetrahydrocarbyl phosphoniumphenoxide salt complexed with tetrahydrocarbyl phosphonium hydroxidewill be produced. Of course, if a smaller excess of the phosphoniumhydroxide is employed, all of the salt will not be complexed. Inparticular, such complexes have been observed where the phenol reactantis dihydric or polyhydric, such as bisphenol A or bisphenol S. Generallythe uncomplexed salt can be recovered by treating the solid, phosphoniumhydroxide complex with acetone. These phosphonium hydroxide complexesare in some instances somewhat less stable than the correspondingtetrahydrocarbyl phosphonium phenoxide salt. For example, atriphenylethyl phosphonium salt of bisphenol A complexed with thecorresponding phosphonium hydroxide had a half-life of three days at 60°C. in a 50 weight percent methanol solution. On the other hand, thecorresponding phosphonium salt of bisphenol S complexed withtriphenylethyl phosphonium hydroxide did not decompose to ethyl diphenylphosphine oxide to any significant degree during a 25-day period at 60°C. in a methanol solution. The aforementioned tetrahydrocarbylphosphonium hydroxide complexes are advantageous as advancementcatalysts, because they are generally more soluble in organic solvents,such as methanol, than are the tetrahydrocarbyl phosphonium phenoxidesalts. Hence, these complexes are more readily dispersed in anadvancement reaction medium containing an organic solvent.

If the phenol reactant has a pKa (of the first hydroxyl groupdeprotonated) greater than about 7.5, for example bisphenol A (pKa10.0), then a phenol complex (formulae III or VII) of the phosphoniumsalt is preferentially isolated from the reaction of the phenol with nomore than an equimolar amount of the phosphonium hydroxide. This solidphenol complex is termed a 1:2 salt because one mole of the phosphoniumcation is present with two moles of the phenol (whether as a phenoxideanion or phenol adduct). On the other hand, if the phenol reactant has apKa less than about 7.5, for example,2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol (pKa 6.8), thetetrahydrocarbyl phosphonium phenoxide salt or di(tetrahydrocarbylphosphonium)bisphenoxide salt or its phenol complex will be thepredominant product isolated. These products are 1:1 phosphonium salts.A large number of acid dissociation constant values are listed in thechapter by H. C. Brown et al. in "Determination of Organic Structures byPhysical Methods", Academic Press (1955), edited by E. A. Braude and F.C. Nachod, which is herein incorporated by reference. The analyticaldata available does not resolve whether the tetrahydrocarbyl phosphoniumphenoxide salt or the di(tetrahydrocarbyl phosphonium)bisphenoxide saltor a phenol complex predominates or is the sole species present atequilibrium in a solution.

The phosphonium phenoxide salts and their phenol and phosphoniumhydroxide complexes are generally white or light-yellow, crystallinesolids having distinct melting points and low vapor pressure. Thesesolids are generally soluble or slightly soluble in moderately polarsolvents, such as acetone, methanol, ethanol, phenol, isopropanol,liquid epoxy resins and the like. These compounds are also generallyinsoluble in benzene, toluene and water.

Epoxide Reactants

The vicinal epoxide reactants are organic compounds bearing one or moremoieties corresponding to the formula ##STR5## The alkylene oxides offrom 2 to about 24 carbon atoms, the epihalohydrins and the epoxy resinsare perhaps the best known and most widely used members of the genus.Ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide andepichlorohydrin are the preferred monoepoxides. These alkylene oxidescan be reacted with monohydric phenols to prepare useful alkylene glycolphenyl ethers, e.g., (C₆ H₅)--OCH₂ CH₂ --OH, in the presence of theabove-described catalysts. Similarly, monoepoxides can be reacted withcarboxylic acids and anhydrides to prepare other useful products.

The most useful epoxy reactants are the polyepoxides, particularly epoxyresins. These polyepoxides are reacted with polyhydric phenols(compounds having more than one phenolic hydroxy group) to form aphenolic hydroxy ether in the so-called advancement reaction. Thepolyepoxide reactants are organic compounds possessing more than one1,2-epoxide group per molecule. These polyepoxides can be saturated orunsaturated aliphatic or cycloaliphatic, aromatic or heterocyclic innature. Additionally, the polyepoxides can bear substituents which areinert in the advancement reaction, such as ether or halogen moieties.

The polyepoxides are conveniently described in terms of epoxy equivalentvalues, as defined in U.S. Pat. No. 2,633,458. The polyepoxides used inthe subject advancement reaction are those having an epoxy equivalencygreater than 1.0.

Various examples of polyepoxides that may be used in the invention aregiven in U.S. Pat. No. 2,633,458 and it is to be understood that so muchof the disclosure of that patent relative to examples of polyepoxides isincorporated by reference into this specification.

Other examples of polyepoxides include the glycidyl ethers of novolacresins, i.e., phenol-aldehyde condensates. Preferred resins of this typeare those of the formula: ##STR6## wherein each R' independently ishydrogen or an alkyl radical and n has an average value of from about0.1 to about 10, preferably from about 1 to about 2. Preparation ofthese polyepoxides is illustrated in U.S. Pat. Nos. 2,616,099 and2,658,885.

The preferred polyepoxides are those represented by the general formula##STR7## wherein R₅, R₆, R₇ and R₈ are each independently selected fromhydrogen, bromine and chlorine and wherein Z is selected from oxygen,sulfur, --SO--, --SO₂ --, bivalent hydrocarbon radicals containing up toabout 10 carbon atoms, oxygen-, sulfur- and nitrogen-containinghydrocarbon radicals, such as --OR'O--, --OR'--O--R'--O--, --S--R'--S--,and ##STR8## wherein R' is a bivalent hydrocarbon radical at eachoccurrence. "Z" preferably is an alkylene or alkylidine group havingfrom about 1 to about 4 carbon atoms.

Other examples of polyepoxides include the epoxidized esters of thepolyethylenically unsaturated monocarboxylic acids, such as epoxidizedlinseed, soybean, perilla, oiticica, tung, walnut and dehydrated castoroil, methyl linoleate, butyl linoleate, ethyl 9,12-octadecanedioate,butyl 9,12,15-octadecanetrioate, butyl oleostearate, mono- ordiglycerides of tung oil, monoglycerides of soybean oil, sunflower oil,rapeseed oil, hempseed oil, sardine oil, cottonseed oil, and the like.

Another group of the epoxy-containing materials used in the process ofthe invention include the epoxidized esters of unsaturated monohydricalcohols and polycarboxylic acids, such as, for example, diglycidylphthalate, diglycidyl adipate, diglycidyl isophthalate,di(2,3-epoxybutyl)adipate, di(2,3-epoxybutyl)oxalate,di(2,3-epoxyhexyl)succinate, di(3,4-epoxybutyl)maleate,di(2,3-epoxyoctyl)pimelate, di(2,3-epoxybutyl)phthalate,di(2,3-epoxyoctyl)tetrahydrophthalate, di(4,5-epoxydodecyl)maleate,di(2,3-epoxybutyl)terephthalate, di(2,3-epoxypentyl)thiodipropionate,di(5,6-epoxytetradecyl)diphenyldicarboxylate,di(3,4-epoxyheptyl)sulfonyldibutyrate,tri(2,3-epoxybutyl)1,2,4-butanetricarboxylate,di(5,6-epoxypentadecyl)tartrate, di(4,5-epoxytetradecyl)maleate,di(2,3-epoxybutyl)azelate, di(3,4-epoxybutyl)citrate,di(5,6-epoxyoctyl)cyclohexane-1,3-dicarboxylate,di(4,5-epoxyoctadecyl)malonate.

Another group of the epoxy-containing materials include those epoxidizedesters of unsaturated alcohols and unsaturated carboxylic acids, such asglycidyl glycidate, 2,3-epoxybutyl 3,4-epoxypentanoate; 3,4-epoxyhexyl3,4-epoxypentanoate; 3,4-epoxy-6-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexane carboxylate.

Still another group of the epoxy-containing materials includesepoxidized derivatives of polyethylenically unsaturated polycarboxylicacids, such as, for example, dimethyl 8,9,12,13-diepoxyeicosanedioate;dibutyl 7,8,11,12-diepoxyoctadecanedioate; dioctyl10,11-diethyl-8,9,12,13-diepoxyeicosanedioate; dihexyl6,7,10,11-diepoxyhexadecanedioate; didecyl9-epoxyethyl-10,11-epoxyoctadecanedioate; dibutyl3-butyl-3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate; dicyclohexyl3,4,5,6-diepoxycyclohexane-1,2-dicarboxylate; dibenzyl1,2,4,5-diepoxycyclohexane-1,2-dicarboxylate and diethyl5,6,10,11-diepoxyoctadecyl succinate.

Still another group comprises the epoxidized polyethylenicallyunsaturated hydrocarbons, such as epoxidized2,2-bis(2-cyclohexenyl)propane, epoxidized vinyl cyclohexene andepoxidized dimer of cyclopentadiene.

Phenolic Reactants

The phenolic reactants are organic compounds having one or more hydroxylgroups attached to an aromatic carbocyclic nucleus. This class ofcompounds therefore includes phenol, alpha and beta naphthol, o-, m-, orp-chlorophenol, alkylated derivatives of phenol (e.g. o-methyl-,3,5-dimethyl-, p-t-butyl- and p-nonylphenol) and other monohydricphenols as well as polyhydric phenols, such as resorcinol, hydroquinone,etc.

The polyhydric phenols bearing from 2 to 6 hydroxyl groups and havingfrom 6 to about 30 carbon atoms are particularly useful as reactants inthe reaction with epoxy resins to form high molecular weight resins.Representative of these preferred phenols are2,4',4"-tri(hydroxyphenyl)methane, phenolphthalein and the like.Particularly preferred as phenol reactants are those compoundscorresponding to formula VIII. The most preferred phenols are bisphenolA, bisphenol F, 2,2',6,6'-tetrachlorobisphenol A,2,2',6,6'-tetrabromobisphenol A, and bisphenol S.

The Carboxylic Acid Reactants

The organic carboxylic acids and anhydrides are likewise well known. Theacids bear one or more carboxyl groups on the organic nucleus. Theanhydrides are prepared from such carboxylic acids by the removal ofwater therefrom in an intra- or intermolecular condensation. This classof compounds therefore includes acetic, propionic, octanoic, stearic,acrylic, methacrylic, oleic, benzoic, phthalic, isophthalic, maleic,succinic, adipic, itaconic, polyacrylic and polymethacrylic acids, andthe like, and anhydrides thereof, such as acetic anhydride, phthalicanhydride, hexahydrophthalic anhydride, etc.

A preferred subclass of acids is comprised of members which are usefulin cross linking epoxy resins. The members of this subclass are normallydi- or tribasic acids, or anhydrides thereof, and are preferably liquidor low melting solids such as succinic, maleic, or hexahydrophthalicacids or anhydrides and the like. Other such acids and anhydrides areshown, for example, in U.S. Pat. No. 2,970,983 and U.S. Pat. No.3,547,885.

Process for Reacting Epoxide and Phenol

The reaction conditions employed in the process may be varied.Generally, however, convenient rates of reaction are obtained atreaction temperatures in the range of from about 50° C. to about 300° C.and reaction pressures ranging from about atmospheric to about 150 psig.

The ratio of the epoxide to the phenol or carboxylic acid or anhydridereactants to be employed in the process may vary over a wide rangedepending upon the type of reactants and the type of product desired.For example, if a product terminated with a phenolic ether group isdesired, one would employ an excess of the phenol in the process.

The amount of the phosphonium catalyst employed in the process of thisinvention can likewise vary over a wide range, so long as a catalyticamount is present. In general, the catalyst is added in amounts of fromabout 0.001 percent to about 10 percent, preferably from about 0.05percent to about 5 percent, by weight of the reactants.

The reaction may be conducted in the presence or absence of solvents ordiluents, but is conveniently conducted in a liquid phase. In mostcases, the reactants will be liquid or low melting solids and thereaction may be at least initially easily effected without the additionof solvents or diluents. As the advancement reaction proceeds and theaverage molecular weight of the product increases, the reaction mixturebecomes progressively more viscous or may solidify. To maintainefficient blending of the reaction mixture, it may be necessary to adddiluents, increase the temperature of the reaction mixture to the fusionpoint of the reactants or to utilize very efficient blending means.Suitable diluents are those organic compounds which are inert to thereactants and in the liquid phase at the reaction temperature, forexample, ethylene glycol ethyl ether, methyl ethyl ketone, acetone,xylene, toluene, cyclohexane and the like. The diluent is desirablysubstantially free of impurities which will decrease the activity of thecatalyst, such as hydrogen peroxide or uncomplexed transition metalions.

If solvents are employed in the reaction and the resulting product is tobe used for coating purposes, the solvent may be retained in thereaction mixture. Otherwise, the solvent can be removed by any suitablemethod such as distillation and the like.

One particularly advantageous embodiment of the instant process is theuse of tetrahydrocarbyl phosphonium salts of polyhydric phenols as acatalyst in the advancement reaction to produce ultra-high molecularweight resins and polymers. Advantageously, the phenoxide anion of thecatalyst is the conjugate base or diconjugate base of a phenolcorresonding to Formula VII. To produce the ultra-high molecular weightresins relatively greater catalyst loadings must be employed than toproduce resins of molecular weights less than about 100,000 molecularweight with these same catalysts. The advancement reaction can beadvantageously conducted in a high boiling, inert, organic diluent, suchas a derivative of ethylene glycol, for example ethylene glycol ethylether and the like. Desirably, substantially equivalent quantities ofpolyhydric phenol and polyepoxide reactants should be employed in theoverall reaction (i.e., no more than about 2 percent excess of eitherreactant). As the reaction between the polyepoxide and the polyhydricphenol approaches completion, it is desirable, but not essential, tointroduce sufficient tetrabromobisphenol A to react the vicinal epoxygroups completely and to increase molecular weight of the product in themanner taught in U.S. Pat. No. 4,104,257.

Advancement Reaction Products

The products obtained according to the above process of reacting apolyepoxide with a phenol in the presence of the desired phosphoniumcatalysts in a process are phenolic hydroxy ether compounds. Theirphysical characteristics will depend upon the reactants and proportionsemployed. In general, the products will vary from liquids to solids, andin the case of the high molecular weight resins will vary from viscousliquids to hard solids. The products will possess an aliphatic OH groupformed by each reaction of an epoxide and a phenolic OH group, and canbe further reacted through this group if desired. The polyfunctionalreactants will also give products terminated in phenolic OH groupsand/or epoxy groups, and these will be available for further reaction.

The control of the equivalent ratio of the polyepoxides and polyhydricphenols during the advancement reaction permits the preparation of avariety of products. Those products which use an excess of thepolyepoxide in their preparation will be terminated in epoxy groups andcan be used as polyepoxides in known reactions of polyepoxides withcuring agents and the like. The high molecular weight polyepoxides areparticularly useful in preparing surface coatings, adhesives, laminates,filament windings, coatings for highways and airfields, structuralapplications, formation of foams and the like. Those prepared from thehalogenated polyhydric phenols as shown hereinafter are particularlyuseful as flame proofing resins for forming laminates, coatings and thelike. The ultra-high molecular weight product terminated with a phenolicether group approaches an engineering thermoplastic, like polycarbonate,in some of its properties and is particularly suited to such uses as anautomotive undercoating, films or molded articles. This novel polymer islinear or substantially linear, consists essentially ofoxyarylene-oxy(1,3-(2-hydroxy)alkylene) units (wherein the arylenemoiety is the aromatic portion of the polyhydric phenol reactant) andsaid polymer has a weight average molecular weight of at least about100,000. The polymeric product can be used as produced by the in-situprocess or the polymer can be precipitated from methanol to removecatalyst by-products and monomeric impurities.

The reaction products terminated in epoxy groups can also be used toprepare vinyl ester resins. Vinyl ester resins are described in U.S.Pat. No. 3,367,992 wherein dicarboxylic acid half esters of hydroxyalkylacrylates or methacrylates are reacted with polyepoxide resins. Bowen inU.S. Pat. Nos. 3,066,112 and 3,179,623 describes the preparation ofvinyl ester resins from unsaturated monocarboxylic acids such as acrylicand methacrylic acid. Vinyl ester resins based on epoxy novolac resinsare described in U.S. Pat. No. 3,301,743 to Fekete et al. Fekete et al.also describe in U.S. Pat. No. 3,256,226 vinyl ester resins wherein themolecular weight of the polyepoxide is increased by reacting adicarboxylic acid with the polyepoxide resin as well as acrylic acid,etc. Other difunctional compounds containing a group which is reactivewith an epoxide group, such as an amine, mercaptan, and the like, may beutilized in place of the dicarboxylic acid. All of the above-describedresins, which contain the characteristic linkages ##STR9## and terminal,polymerizable vinylidene groups, are classified as vinyl ester resins,and are incorporated herein by reference.

The unsaturated monocarboxylic acids which can be reacted with apolyepoxide in the presence of the described catalysts to prepare avinyl ester resin include acrylic acid, methacrylic acid, halogenatedacrylic acid or methacrylic acid, cinnamic acid and the like andmixtures thereof, and hydroxyalkyl acrylate or methacrylate half estersof dicarboxyl acids as described in U.S. Pat. No. 3,367,992 wherein thehydroxyalkyl group preferably has from 2 to 6 carbon atoms.

Precatalyzed Epoxy Resins and Precatalyzed Polyhydric Phenols

Precatalyzed epoxy resin and precatalyzed polyhydric phenol compositionsare of particular commercial interest. Precatalyzed epoxy resincompositions are blends of an epoxy resin and an effective amount of anadvancement catalyst, which when combined with a polyhydric phenol atreactive conditions produce epoxy resins of increased molecular weight.Similarly, precatalyzed polyhydric phenols are blends of a polyhydricphenol and an effective amount of an advancement catalyst. In the caseof a normally solid polyhydric phenol, such as bisphenol A, it isadvisable to first melt the phenol and then to add the catalyst to theliquid phenol to obtain a homogeneous mixture. The catalysts previouslydescribed are particularly suited for this use.

The following examples are illustrative of the present invention and arenot to be construed as limiting the scope thereof in any manner. Allparts and percentages are by weight unless otherwise specified.

EXAMPLE 1

A solution of 100 grams of n-butyl triphenylphosphonium bromide in 40grams of methanol is percolated through a tightly packed column of 509grams of a quaternary ammonium-type, styrene-divinylbenzene anionexchange resin (sold under the tradename Dowex SBR) bearing 3.5milliequivalents per gram of exchangeable hydroxide groups. The methanolsolution is found by conventional methods of analysis to contain 20.7percent of n-butyl triphenyl phosphonium hydroxide salt and less than0.05 percent bromine.

A solution of 78.8 grams (0.145 mole) of 2,2',6,6'-tetrabromobisphenol Ain 50 grams of methanol is added with stirring at 20° C. to 48.8 grams(0.145 mole) of the n-butyl triphenyl phosphonium hydroxide salt in236.0 grams of methanol solvent. After stirring the reaction mixture forthirty minutes, the mixture is filtered to collect a white precipitate.The collected precipitate is dried to yield 122.5 grams of a crudeproduct having a melting point of 218° C.-220° C. The product is thenwashed with acetone. Conventional methods of analysis (infraredspectroscopy, elemental analysis and proton, carbon-13 and phosphorusnuclear magnetic resonance) are utilized to identify the product as a1:1 n-butyl triphenyl phosphonium salt of 2,2',6,6'-tetrabromobisphenolA. The yield of the identified product based on the correspondingphosphonium hydroxide salt is 98.0 mole percent.

EXAMPLE 2

In a manner otherwise similar to that described in Example 1, a methanolsolution of 66.2 grams (0.29 mole) of bisphenol A is added to a stirredmethanol solution containing 48.8 grams (0.145 mole) of the n-butyltriphenyl phosphonium hydroxide salt. A white crystalline precipitate iscollected and dried to a constant weight of 103.97 grams. The meltingpoint of the crude product is 153° C.-155° C. Conventional methods ofanalysis are utilized to identify the product as a 1:2 n-butyl triphenylphosphonium salt complex of bisphenol A. The yield of the identifiedproduct based on the corresponding phosphonium hydroxide salt is 92.4mole percent.

When equimolar amounts of the n-butyl triphenyl phosphonium hydroxidesalt and bisphenol A are employed in the methanol reaction medium a 1:2n-butyl triphenyl phosphonium salt of bisphenol A is still isolated.

EXAMPLE 3

In a manner otherwise similar to that described in Example 1, a methanolsolution of 53.09 grams (0.145 mole) of tetrachlorobisphenol A is addedto 48.8 grams (0.145 mole) of the n-butyl triphenyl phosphoniumhydroxide salt. A white crystalline precipitate, having a dry weight of97.75 grams, is collected. Conventional methods of analysis are utilizedto identify the product as a 1:1 n-butyl triphenyl phosphonium salt of2,2',6,6'-tetrachlorobisphenol A. The yield of the identified product is98.5 mole percent.

EXAMPLE 4

In a manner otherwise similar to that described in Example 1, a methanolsolution of 4.09 grams (0.024 mole) of 2-hydroxybiphenyl is added to astirred methanol solution of 4.06 grams (0.012 mole) of the n-butyltriphenyl phosphonium hydroxide salt. The methanol solvent is distilledfrom the reaction mixture and the remaining 6.64 grams of a light-yellowsolid washed with acetone. The solid is identified by conventionalmethods of analysis as a 1:2 n-butyl triphenyl phosphonium salt complexof 2-hydroxybiphenyl. The yield of the identified product is 84.0 molepercent.

EXAMPLE 5

In a manner otherwise similar to that described in Example 1, a methanolsolution of 3.03 grams (0.024 mole) of 1,3,5-trihydroxybenzene is addedto a stirred methanol solution of 4.06 grams (0.012 mole) of the n-butyltriphenyl phosphonium hydroxide salt. The methanol solvent is distilledfrom the reaction mixture and the remaining 6.7 grams of tan solidwashed with acetone. Conventional methods of analysis are utilized toidentify the product as a 1:2 n-butyl triphenyl phosphonium salt complexof 1,3,5-trihydroxybenzene. The yield of the identified product is 98.0mole percent.

EXAMPLE 6

A solution of 140 grams of tetra(n-butyl)phosphonium bromide in 56 gramsof methanol is percolated through a tightly packed column of 509 gramsof a quaternary ammonium-type, styrene-divinylbenzene anion exchangeresin (sold under the tradename Dowex SBR) bearing 3.5 milliequivalentsper gram of exchangeable hydroxide groups. The column is flushed withadditional quantities of methanol, which are combined with the firstmethanol solution. The resulting methanol solution is determined tocontain 17.0 percent of tetrabutyl phosphonium hydroxide salt.

In a manner otherwise similar to Example 1, a methanol solution of 44.47grams (0.195 mole) of bisphenol A is added to a stirred methanolsolution containing 27 grams (0.0975 mole) of tetrabutyl phosphoniumhydroxide salt. A white crystalline precipitate is collected and driedto a constant weight of 68.1 grams. The melting point of the crudeproduct is 218° C.-221° C. Conventional methods of analysis are utilizedto identify the product as a 1:2 tetra(n-butyl)phosphonium salt ofbisphenol A. The yield of the identified product is 95.3 mole percent.

EXAMPLES 7-11

In a manner otherwise similar to that described in Example 6, thephenols listed in Table I are reacted with tetra(n-butyl)phosphoniumhydroxide salt. The crude product is then isolated from the methanolreaction mixture, dried and weighed. Conventional methods of analysisare utilized to identify the product and in each instance the product isa tetra(n-butyl)phosphonium salt of the phenol reacted as expected. Themole ratio of the tetra(n-butyl)phosphonium hydroxide salt (R₄ P.sup.⊕⊖OH) to the phenol (HX) added to the reaction mixture, the mole ratio ofthe tetra(n-butyl)phosphonium cation to the total phenoxide and phenolin the product salt, the isolated yield of the product in mole percentand the pKa of the phenol reactant are also tabulated in Table I.

                                      TABLE I                                     __________________________________________________________________________                Reaction                                                                              Salt                                                                  Mole Ratio                                                                            Mole Ratio                                                                             Isolated                                         Example                                                                            Phenol R.sub.4 P.sup.⊕⊖ OH:HX                                                    R.sub.4 P.sup.⊕ :(HX + X.sup.⊖)                                            Yield                                                                              pKa                                         __________________________________________________________________________     7   2,2',6,6'-                                                                    Tetrabromo                                                                    bisphenol A                                                                          1:1     1:1      81.5 6.8                                          8   Pentachloro-                                                                         1:1     1:1      97.0 4.6                                              phenol                                                                    9   4,6-Dinitro-                                                                  2-sec-butyl-                                                                  phenol 1:1     1:1      94.0 4.4                                         10   4,4'-Thio-                                                                    diphenol                                                                             1:2     1:2      98.0 10.3                                        11   4-t-Butyl-                                                                    phenol 1:2     1:2      62.4 *                                           12   4,4'-sulfo-                                                                          1:2     1:2      97.5 7.8                                              nyldiphenol                                                              __________________________________________________________________________     *Not determined                                                          

EXAMPLES 13-22

In a manner otherwise similar to that described in Example 1, severaltetrahydrocarbyl phosphonium chloride (R₄ P.sup.⊕ Cl.sup.⊖) salts listedin Table II are percolated through an ion-exchange column to produce thecorresponding hydroxide salts. These tetrahydrocarbyl phosphoniumhydroxide salts are then reacted with the phenol reactants (HX)tabulated in Table II in the appropriate mole ratios to produce thecorresponding tetrahydrocarbyl phosphonium salt of the phenol reacted,as is confirmed by conventional methods of analysis. Other parametersand results of interest are also tabulated in Table II.

                  TABLE II                                                        ______________________________________                                                                   Salt                                               Ex-                        Mole Ratio Isolated                                ample R.sub.4 P.sup.⊕ Cl.sup.⊖                                                    Phenol     R.sub.4 P.sup.⊕ :(HX + X.sup.⊖)                                              Yield                                   ______________________________________                                        13    Benzyltri-                                                                    phenyl    Bisphenol A                                                                              1:2        95.0                                          P.sup.⊕ Cl.sup.⊖                                            14    Benzyltri-                                                                              2,2',6,6'-                                                          phenyl    tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        97.0                                    15    Methyltri-                                                                              2,2',6,6'-                                                          phenyl    tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        96.5                                    16    Methyl(tri-                                                                             2,2',6,6'-                                                          n-butyl)  tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        *                                       17    Methyl(tri-                                                                   n-butyl)                                                                      P.sup.⊕ Cl⊖                                                                 Bisphenol A                                                                              1:2        *                                       18    Benzyl(tri-                                                                   n-butyl)                                                                      P.sup.⊕ Cl.sup.⊖                                                            Bisphenol A                                                                              1:2        *                                       19    Benzyl(tri-                                                                             2,2',6,6'-                                                          n-butyl)  tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        *                                       20    Tetra-    2,2',6,6'-                                                          phenyl    tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        *                                       21    Tetra-                                                                        phenyl                                                                        P.sup.⊕ Cl                                                                          Bisphenol A                                                                              1:2        *                                       22    Ethyltri- 2,2',6,6'-                                                          phenyl    tetrabromo-                                                         P.sup.⊕ Cl.sup.⊖                                                            bisphenol A                                                                              1:1        *                                       ______________________________________                                         *Not determined.                                                         

EXAMPLES 23-26

A stirred methanol solution containing 45 grams (0.113 mole) of n-butyltriphenyl phosphonium bromide salt is contacted for 10 minutessequentially with five 31-gram portions of a quaternary ammonium-type,styrene-divinylbenzene anion-exchange resin bearing 3.5 milliequivalentsof exchangeable hydroxide groups per gram. After each contact, themethanol solution is separated from the resin and combined with methanolwashes of the partially exchanged resin. This procedure produced an 8percent solution of n-butyl triphenyl phosphonium hydroxide salt.

In a manner otherwise similar to that described in Example 1, thephenols listed in Table III are reacted with the n-butyl triphenylphosphonium hydroxide salt prepared as described immediately above. Thecrude product is then isolated from the methanol reaction mixture, driedand weighed. Conventional methods of analysis are utilized to identifythe product and in each instance the product is an n-butyl triphenylphosphonium salt of the phenol reacted as expected. The mole ratio ofthe phosphonium hydroxide salt to the phenol added to the reactionmixture, the mole ratio of the phosphonium cation to the total phenoxideand phenol in the product salt and the isolated yield of the product inmole percent are tabulated in Table III.

                  TABLE III                                                       ______________________________________                                                        Reaction    Salt       Iso-                                   Ex-             Mole Ratio  Mole Ratio lated                                  ample Phenol    R.sub.4 P.sup.⊕ OH:HX                                                                 R.sub.4 P.sup.⊕ :(HX + X.sup.⊖)                                              Yield                                  ______________________________________                                        23    4,4'-Di-                                                                      hydroxy-                                                                      diphenyl-                                                                     ether       1:2.4     1:2        76                                     24    Phenol-                                                                       phthalein 1:2         1:2        76                                     25    Resorcinol                                                                              1:2         1:2        90                                     26    2,2'-Di-                                                                      hydroxy-                                                                      biphenyl  1:2         1:2        76                                     ______________________________________                                    

EXAMPLE 27

An aqueous solution of 50 percent sodium hydroxide (5.02 grams, 0.0627mole) at 20° C. is added to a stirred reaction mixture of 25 grams(0.0626 mole) n-butyltriphenyl phosphonium bromide in 37.5 milliliters(ml) of methanol cooled to a temperature of 5° C. The rate of sodiumhydroxide addition is controlled so that the temperature of the reactionmixture does not exceed 15° C. After addition of the sodium hydroxide iscomplete, the temperature of the stirred reaction mixture is permittedto rise to 18° C. over a period of 15 minutes. A solution of 28.54 grams(0.125 mole) of bisphenol A in 34.0 ml of methanol is rapidly added at20° C. to the stirred reaction mixture. The reaction mixture is stirredfor an additional 10 minutes, followed by the addition of 12.5 grams ofdeionized water to the mixture, and stirring for 60 more minutes. Awhite crystalline precipitate is recovered by filtration of the reactionmixture. This crude product is washed with deionized water and dried toa weight of 46.0 grams. Conventional methods of analysis are utilized toidentify the product as a 1:2 n-butyl triphenyl phosphonium salt complexof bisphenol A. The yield of the product based on the correspondingphosphonium hydroxide salt is 92.7 mole percent.

EXAMPLE 28

A solution of 28.54 grams (0.125 mole) of bisphenol A in 34.0 ml ofmethanol at 20° C. is added to a stirred reaction mixture of 25 grams ofn-butyl triphenyl phosphonium bromide in 37.5 ml of methanol. An aqueoussolution of 50 percent sodium hydroxide (5.02 grams, 0.0627 mole) at 20°C. is then added to the reaction mixture with cooling and at a slow rateso that the temperature of the mixture does not exceed 25° C. Thereaction mixture is stirred for an additional 10 minutes, followed bythe addition of 12.5 grams of deionized water to the mixture andstirring for 60 more minutes. A white crystalline precipitate isrecovered by filtration of the reaction mixture. This crude product iswashed with deionized water and dried to a weight of 48.4 grams.Conventional methods of analysis are utilized to identify the product asa 1:2 n-butyltriphenyl phosphonium salt complex of bisphenol A. Theyield of the product based on the corresponding phosphonium hydroxidesalt is 96 mole percent.

EXAMPLE 29

To a reaction vessel equipped with means for stirring and temperatureindication is charged 141.37 grams of the diglycidyl ether of bisphenolA (DGEBA) having an epoxy equivalent weight of 183, 82.08 grams ofbisphenol A and 74.5 grams of ethylene glycol ethyl ether. The DGEBAcontains 0.375 percent total chlorine and 311 ppm of hydrolyzablechlorine. The reaction mixture is heated to about 50° C. and then 2.59grams (1.11 percent of reactants) of the 1:1 n-butyl triphenylphosphonium salt of 2,2',6,6'-tetrabromobisphenol A described in Example1 is introduced with stirring. The stirred reaction mixture is rapidlyheated to 110° C. and then more slowly heated over a period of 30minutes to 130° C. and maintained at the latter temperature for 165minutes. A small sample of the reaction mixture is analyzed byconventional methods and it is determined that about 95.5 percent of theepoxy moieties and 98.7 percent of the phenolic hydroxyl groups havereacted.

Next 8.16 grams of 2,2',6,6'-tetrabromobisphenol A and 50.2 grams ofethylene glycol ethyl ether is added to the reaction mixture. It isdesirable to utilize as little of the ethylene glycol ethyl ethersolvent as is possible to maximize the weight-average molecular weightof the product resin; however, as the reaction mixture becomes tooviscous to stir effectively, it is necessary to add additional amountsof the solvent. After 50 minutes at 130° C., it is necessary to add anadditional 29.7 grams of ethylene glycol ethyl ether to the reactionmixture and after 65 additional minutes another 77.4 grams of solvent isadded. The reaction mixture is stirred for 65 more minutes at 130° C.,then 463 grams of ethylene glycol ethyl ether is added to the reactionmixture and the mixture is stirred to effect a homogeneous solution ofthe resin product. The weight-average molecular weight of the productresin in the solution as determined by gel permeation chromatography(GPC) is 123,825.

The homogeneous resin product solution at 25° C. is removed and dilutedwith an equal weight of ethylene glycol ethyl ether. This dilute productsolution is added with vigorous stirring to 3,500 grams of methanol. Theresulting resin product slurry is stirred for ten minutes and then theresin is collected by filtration. The resin is dried to a constantweight of 220 grams. The precipitated resin is determined by gelpermeation chromatography to possess a weight-average molecular weight(M_(w)) of 120,192 and a number-average molecular weight of 14,855(M_(n)).

About 37 grams of this ultra-high molecular weight (UHMW) resin is thenmolded into a 2.75"×5" by one-eighth inch thick sheet in a heated pressat a ram pressure of 15 tons. This sheet is then cut into stripssuitable for testing the tensile strength, impact strength, flexuralstrength and hardness of the molded resin. Test strips of ahigh-molecular weight epoxy resin (M_(w) =39,800, M_(n) =7,000) soldcommercially by Union Carbide Company under the tradename "PKHH" areprepared in a like manner for purposes of comparison. All tests areperformed in accordance with standard methods approved by the AmericanSociety for Testing and Materials (ASTM) in Part 27. The moldingtemperature for each sheet and the relevant test data is set out inTable IV.

                  TABLE IV                                                        ______________________________________                                                             Materials Tested                                                     Property                UHMW                                      ASTM Test#  Tested         PKHH*    Resin                                     ______________________________________                                          --        Molding Temperature                                                                          177° C.                                                                         240° C.                            D-638-68    Yield Tensile                                                                 Strength (psi) 8,684    9,980                                       "         Yield Elongation (%)                                                                         3.33     3.84                                      D-790-66 Method I                                                                         Flexural Strength                                                                            14,679   15,866                                                (psi)                                                               "         Flexural Modulus of                                                           Elasticity (psi)                                                                             419,900  396,900                                   D-2583-67   Barcol Hardness                                                                              14       9                                         D-256-56    Izod Impact Strength                                              Method A    (foot-pounds/inch)                                                                           1.63     1.21                                      ______________________________________                                         *Not an embodiment of this invention.                                         PKHH -- tradename of a high molecular weight epoxy resin sold by Union        Carbide Company                                                          

EXAMPLES 30-35

In the manner described in Example 29, a reaction vessel is charged withDGEBA, bisphenol A and an ethylene glycol ethyl ether solvent. Thereaction mixture is heated to 50° C. and then a quantity of ann-butyltriphenyl or triphenylmethyl phosphonium phenoxide catalyst (from0.65 to 1.70 percent of the reactants) as tabulated in Table IV isintroduced. The general procedure for preparing a 25 percent solution ofan ultra high molecular weight resin product in an ethylene glycol ethylether described in Example 29 is then followed. The weight-averagemolecular weight of the product resin in the solution as determined byGPC is also determined and tabulated.

                  TABLE V                                                         ______________________________________                                                                 Catalyst                                             Example  P.sup.⊕ Phenoxide Salt                                                                    (Wt. %)  M.sub.w                                     ______________________________________                                        30       1:2 (C.sub.6 H.sub.5).sub.3 P.sup.⊕ (C.sub.4 H.sub.9)                                     0.71      79,640                                              Salt of Bisphenol A                                                  31       1:2 (C.sub.6 H.sub.5).sub.3 P.sup.⊕  (CH.sub.3)                                           0.65      70,740                                              Salt of Bisphenol A                                                  32       1:1 (C.sub.6 H.sub.5).sub.3 P.sup.⊕  (C.sub.4 H.sub.9)                                    0.65      71,050                                              Salt of Tetrabromo-                                                           bisphenol A                                                          33       1:1 (C.sub.6 H.sub.5).sub.3 P.sup.⊕ (C.sub.4 H.sub.9)                                     1.68     142,210                                              Salt of Tetrabromo-                                                           bisphenol A                                                          34       1:1 (C.sub.6 H.sub.5).sub.3 P.sup.⊕ (C.sub.4 H.sub.9)                                     1.70     121,930                                              Salt of Tetrabromo-                                                           bisphenol A                                                          35       1:1 (C.sub.6 H.sub.5).sub.3 P.sup.⊕ (C.sub.4 H.sub.9)                                     1.69     118,810                                              Salt of Tetrachloro-                                                          bisphenol A                                                          ______________________________________                                    

The data in Table V suggest that to produce resins having ultra-highmolecular weights relatively greater catalyst loadings must be employedthan used to produce those of relatively lower molecular weights.

EXAMPLE 36

To a reaction vessel equipped with means for stirring, heating andtemperature indication is charged at 20° C. under nitrogen purge with67.0 parts of bisphenol A, 133.0 parts of DGEBA having an epoxyequivalent weight (EEW) of 187 and 0.484 parts of a 1:1 n-butyltriphenylphosphonium salt of 2,2',6,6'-tetrabromobisphenol A. This stirredreaction mixture is warmed at a rate of 3° C. per minute to about 150°C. External heating is discontinued at 150° C., but the exotherm of thereaction heats the mixture to a peak temperature of about 222° C. Thereaction mixture is permitted to cool to 160° C. and maintained at thattemperature for 30 minutes.

The observed epoxy content of the resin product determined byconventional wet analysis technique is 2.36 percent, almost as great asthe theoretical epoxy content of a linear advanced epoxy resin 2.39percent. A substantially linear epoxy resin of excellent color isprovided.

EXAMPLE 37

In a manner similar to that described in Example 36 a reaction mixtureof 0.396 parts of 1:2 n-butyltriphenyl phosphonium salt of bisphenol A,64.0 parts of bisphenol A and 136.0 parts of DGEBA is warmed to 150° C.and then allowed to heat in accordance with the reaction exotherm. Thereaction mixture is then permitted to cool from its peak temperature of244° C. to 160° C., where the temperature is maintained for thirtyminutes.

The observed epoxy content of the resin product determined byconventional wet analysis technique is 4.64 percent; almost identical tothe theoretical epoxy content of 4.65 percent. A substantially linearepoxy resin of excellent color is provided.

EXAMPLE 38

To a reaction vessel equipped with means for stirring and controllingtemperature is charged at 20° C. under a nitrogen purge a mixture of 87parts of bisphenol A and 200 parts of DGEBA having an EEW of 187.7. Thisstirred reaction mixture is warmed to a temperature of 100° C. over aperiod of 30 minutes and then 0.428 parts of a 1:2 n-butyltriphenylphosphonium salt of bisphenol A is introduced. The temperature of themixture is controlled during the reaction so that it does not exceed200° C. After the exothermic reaction slows, the mixture is heated at190° C. for 2 hours.

The observed epoxy content of the resin product determined byconventional wet analysis technique is 4.34 percent; almost as great asthe theoretical epoxy content of 4.65 percent. A substantially linearepoxy resin of excellent color is provided. This resin differs from theresin prepared in Example 37 in that molded articles produced from theformer have somewhat better heat distortion properties than thoseproduced from the latter resin.

EXAMPLE 39

To a reaction vessel equipped with means for stirring and temperatureindication is charged at 20° C. under nitrogen purge 10.3 grams (0.05mole) of 4-t-butylphenyl glycidyl ether, 3.6 grams (0.05 mole) ofacrylic acid and 0.014 gram of the 1:2 n-butyltriphenyl phosphonium saltof bisphenol A. The reaction mixture is stirred at a temperature of 115°C. for a period of five hours. The reaction mixture is titrated withbase at the end of the reaction period and less than 1 percent of theacrylic acid added is determined to be unreacted. Infrared spectroscopyand other conventional methods of analysis are utilized to identify theproduct as corresponding to the formula ##STR10##

In contrast, only a 28 percent yield of product is obtained in a similarexperiment conducted without the catalyst. This example demonstrates theefficacy of the tetrahydrocarbyl phosphonium phenoxide salt in promotingthe reaction of a carboxylic acid with an epoxide.

EXAMPLE 40

To a reaction vessel equipped with means for stirring and temperatureindication is charged at 20° C. under nitrogen purge 9.4 grams (0.1mole) of phenol, 4.84 grams (0.11 mole) of ethylene oxide and 0.014 gramof the 1:2 n-butyltriphenyl phosphonium salt of bisphenol A. Thereaction mixture is stirred at a temperature of 150° C. for a period of3 hours. The reaction mixture is first cooled and then analyzed byconventional methods of analysis. The product is identified as 93.8percent ethylene glycol phenyl ether and 6.0 percent diethylene glycolphenyl ether. The conversion of the phenol to the above-identifiedproduct is 99.7 percent.

EXAMPLE 41

To a reaction vessel equipped with means for stirring and temperatureindication is charged at 20° C. 423.9 grams of the diglycidyl ether ofbisphenol A (DGEBA) having an epoxy equivalent weight of 188.73 and136.7 grams of bisphenol A. The reaction mixture is heated to 70° C. andthen 0.57 grams of 1:1 n-butyltriphenyl phosphonium salt of2,2',6,6'-tetrabromobisphenol A is introduced with stirring. The mixtureis rapidly heated to 90° C. and then more slowly over a period of 30minutes is heated to 150° C. The reaction mixture is maintained at 150°C. for 1.5 hours and then allowed to cool. Another 143.21 grams of DGEBAis added to the reaction mixture at a temperature of 120° C. After 10minutes, a small sample of the reaction mixture is analyzed byconventional methods to determine an epoxide content of 11.08 percentand an epoxy equivalent weight of 388.01. Thus, the epoxy resin has beenpartially advanced.

The partially advanced epoxy resin product is purged with air and thencombined with 0.19 gram hydroquinone (a vinyl polymerization inhibitor),155.59 grams methacrylic acid and 1.1 grams tridimethyl aminomethylphenol (a curing accelerator) at 115° C. After 5.5 hours, a sample ofthe vinyl ester resin is taken and 850 grams of styrene is introduced tothe remaining vinyl ester resin to reduce the viscosity of the productmixture. Analysis of the sample of vinyl ester resin product byconventional methods indicates an acid content of 0.97 percent and anepoxide content of 0.83 percent.

The styrene/vinyl ester resin mixture is cured at a temperature of about75° C. in the presence of cobalt naphthenate and methyl ethyl ketoneperoxide in the conventional manner. The cured vinyl ester resin-styrenecopolymer possesses the physical properties tabulated in Table VI.

                  TABLE VI                                                        ______________________________________                                        ASTM Test #   Property Tested                                                                            Test Result                                        ______________________________________                                        D-638-68      Yield Tensile                                                                              12,278 psi                                                       Strength                                                        D-638-68      Yield Elongation                                                                           5.52%                                              D-790-66      Flexural Strength                                                                          12,193 psi                                         Method                                                                        D-790-66      Flexural Modulus                                                                           554,000 psi                                        Method        of Elasticity                                                   D-2583-67     Barcol Hardness                                                                            26.2                                               ______________________________________                                    

It is apparent from the data tabulated in Table VI that the vinyl esterresins produced from epoxy resins advanced with the catalysts of thisinvention possess useful properties.

EXAMPLE 42

A methanol solution of sodium hydroxide (4.0 grams, 0.1 mole) at 20° C.is added slowly to a stirred reaction mixture of ethyltriphenylphosphonium bromide (37.13 grams, 0.1 mole) in 37.0 grams of methanolcooled to a reaction temperature of 10° C. The rate of sodium hydroxideaddition is controlled, so that the temperature of the reaction mixturedoes not exceed 10° C. After addition of the sodium hydroxide iscomplete, the reaction mixture is stirred for one hour and then filteredthrough a sintered glass funnel. The recovered solid, sodium bromide, iswashed with cold, anhydrous methanol and dried to yield 10.0 grams(97.17 percent yield).

A methanol solution of bisphenol A (11.4 grams, 0.05 mole) at 20° C. isadded slowly to the stirred filtrate containing ethyltriphenylphosphonium hydroxide at 10° C. After stirring at 10° C. for one hour,the excess methanol solvent is removed by vacuum distillation technique(50° C., 0.1 mm) to yield a light-yellow solid; the reaction mixtureyielded 40.1 grams (97.0 percent) of the product. Conventional methodsof analysis are used to identify the product as an ethyltriphenylphosphonium salt of bisphenol A complexed with an ethyltriphenylphosphonium hydroxide.

This solid product is treated by stirring it in acetone at 25° C. forten minutes. The acetone is filtered to recover 28.0 grams of a whitesolid product, which is identified as the uncomplexed ethyltriphenylphosphonium salt of bisphenol A.

EXAMPLE 43

A methanol solution of sodium hydroxide (4.0 grams, 0.1 mole) at 20° C.is added slowly to a stirred reaction mixture of ethyltriphenylphosphonium bromide (37.13 grams, 0.1 mole) in 37.0 grams of methanolcooled to a reaction temperature of 10° C. The rate of sodium hydroxideaddition is controlled, so that the temperature of the reaction mixturedoes not exceed 10° C. After addition of the sodium hydroxide iscomplete, the reaction mixture was stirred for one hour and thenfiltered through a medium sintered glass funnel. The recovered solid,sodium bromide, was washed with cold, anhydrous methanol and dried toyield 10.0 grams (97.17 percent yield).

A methanol solution of bisphenol S (12.5 grams, 0.05 mole) at 20° C. isadded slowly to the stirred filtrate containing ethyltriphenylphosphonium hydroxide at 10° C. After stirring at 10° C. for one hour,the excess methanol solvent is removed by vacuum distillation (50° C.,0.1 mm) to yield a light-yellow solid, the reaction mixture yielded41.21 grams (97.0 percent) of product. Conventional methods of analysisare used to identify the product as an ethyltriphenyl phosphonium saltof bisphenol S complexed with an ethyltriphenyl phosphonium hydroxide.

EXAMPLE 44

One gram of the 1:2 n-butyl triphenyl phosphonium salt of bisphenol Aprepared in Example 2 is charged with stirring to a reaction vesselcontaining 1000 grams of DGEBA. The stirred precatalyzed resin ismaintained at a temperature of 50° C. for six weeks, during which timethe viscosity in centipose and the percent epoxide are measured attwo-week intervals. The measured parameters are tabulated in Table VII.

At the end of the six-week period, a sufficient quantity of bisphenol Ais added to the precatalyzed resin, so that at reactive conditions theresin would be predicted by theory to produce one having an epoxycontent of 2.10 percent. The resulting mixture is heated at 160° C. fortwo hours. The observed epoxy content of the resin product determined byconventional wet analysis is 2.12 percent, virtually the same as thetheoretical epoxy content of 2.10 percent.

                  TABLE VII                                                       ______________________________________                                        Time          Viscosity Percent                                               (weeks)       (centipoise)                                                                            Epoxide                                               ______________________________________                                        0             10,372    23.82                                                 2             10,566    23.78                                                 4             10,600    23.80                                                 6             10,622    23.75                                                 ______________________________________                                    

What is claimed is:
 1. A compound represented by the formula ##STR11##or a complex of the compound represented by Formula I with one or moreequivalents of a phenol, H_(m) X, wherein(1) R₁ -R₄ each independentlyis a hydrocarbyl or inertly-substituted hydrocarbyl; (2) X is aphenoxide anion, said anion being a conjugate base of a polyhydricphenol bearing from 2 to 6 nuclear hydroxyl groups and having from about12 to about 30 carbon atoms; and (3) m is the valence of the anion X. 2.The compound defined by claim 1 wherein R₁ -R₄ each independently isphenyl or C₁ to C₁₂ alkyl or inertly-substituted alkyl.
 3. The compounddefined by claim 1 wherein R₁ -R₄ each independently is phenyl or C₁ toC₄ alkyl.
 4. The compound defined by claim 1 wherein R₁ -R₄ eachindependently is phenyl or n-butyl.
 5. The compound defined by claim 1wherein R₁ is an n-butyl or ethyl group and R₂ -R₄ are each phenyl. 6.The compound defined by claim 1, 2 or 5 wherein X is derived from apolyhydric phenol corresponding to phenolphthalein or to the formula##STR12## wherein, (1) each R independently is a hydrogen, halogen,hydrocarbyl, inertly-substituted hydrocarbyl or hydrocarbyloxy group;(2)Y is a single covalent bond, oxygen, sulfur, --CO--, --SO--, --SO₂ -- orlower alkylene or alkylidene of from 1 to 6 carbon atoms, inclusive; and(3) m is the integer 1 or
 2. 7. The compound defined by claim 6 whereineach R independently is hydrogen, chlorine or bromine.
 8. The compounddefined by claim 7 wherein Y is C₁ -C₄ alkylene or alkylidene.
 9. Thecompound defined by claim 8 wherein Y is methylene or isopropylidene.10. The compound defined by claim 6 wherein X is a phenoxide anion ordianion derived from bisphenol A, bisphenol F, phenolphthalein,2,2',6,6'-tetrachlorobisphenol A, bisphenol S, bis(4-hydroxyphenyl),2-hydroxyphenylmethane or 2,2',6,6'-tetrabromobisphenol A.
 11. Thecompound defined by claim 10 wherein X is a phenoxide anion or dianionderived from bisphenol A or 2,2',6,6'-tetrabromobisphenol A.